CN1080635A - The preparation method of methylol hydantoin - Google Patents
The preparation method of methylol hydantoin Download PDFInfo
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- CN1080635A CN1080635A CN93105790A CN93105790A CN1080635A CN 1080635 A CN1080635 A CN 1080635A CN 93105790 A CN93105790 A CN 93105790A CN 93105790 A CN93105790 A CN 93105790A CN 1080635 A CN1080635 A CN 1080635A
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- glycolylurea
- formaldehyde source
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
- C07D233/78—Radicals substituted by oxygen atoms
Abstract
A kind of method for preparing the solid water-free methylol hydantoin is disclosed, but this method comprise the dehydration and heat a kind of moisture agitated medium, obtain a kind of substantially anhydrous stirred melt; In described melt, add a kind of reaction mixture, obtain a kind of molten system; At least a glycolylurea reactant and at least a dehydration formaldehyde source reactant or substantially anhydrous formaldehyde source reactant are reacted in described molten system, remove the water that dereaction generates simultaneously, obtain anhydrous fusion methylol hydantoin; Solidify described fusion methylol acetylurea.Aforesaid method can interrupter method or semi-continuous process enforcement.
Description
The present invention relates to the preparation method of solid water-free methylol hydantoin.The inventive method has been avoided mixing the restriction of relevant processing aspect usually with solid, and can use common Liquid-phase reactor to produce the solid water-free glycolylurea.
Methylol hydantoin is a kind of colourless, tasteless, water-soluble cpds, and can be used as formaldehyde and give material and be used for some goods to the microorganism growth sensitivity.These goods comprise for example liquid washing agent of Industrial products, aqueous based surfactant, soft soap, water-based paint, fabric softening, indoor reodorant/air freshener, polymer emulsion, the used for textiles protective cover, building coating, aqueous gel, seal gum and putty, paper coating latex, water-based ink, wood is sanitas or the like; Also comprise for example makeup of personal hygiene article, shampoo, fat, lotion, powdery product or the like.
For example monomethylol dimethyl hydantoin (MDMH) or dihydroxymethyl T10 (DMDMH) are typically with the form preparation of aqueous solution for methylol hydantoin, and common method for making is to make one mole of DMH and one mole or 2 moles of formaldehyde methylolations.Especially, Foelsh is at US3, and 987, a kind of method of the DMDMH of preparation aqueous solution is disclosed in 184, wherein every mole 5,5-T10 (5,5-DMH) and 1.85-2,4 moles of formaldehyde (aqueous solution) are at the about 7-9 of pH, and reaction is about 20 minutes under about 22 ℃ of-65 ℃ of temperature.
But,, increased the product cost of moisture MDMH and DMDMH solution owing to the expense of solvent and transportation aqueous solution.Therefore, need a kind of dry product.The simplest method of preparation dry product is that methylol hydantoin is isolated from solvent.But sepn process is generally all lengthy time-consuming and comprise one or more procedure of processings.
People such as Farina are at US4, disclose the method for the crystalline methylol hydantoin that preparation does in 908,465, and this method is to make glycolylurea, and formaldehyde source such as Paraformaldehyde 96 and catalyst mix make each component reaction then under heating up.But because reagent is dry mixedly to be heated to extreme temperature then, so required equipment is complicated and be difficult for realizing.
Had been found that the method for liquid phase production solid water-free methylol hydantoin.These methods can be implemented in common liquid processing reactor, and reason is to contain water-bearing media in the initial reactor of filling.In the methods of the invention, reactor never contains complete solid intermediate materials.Therefore, do not need to bear the special dry processing units of reaction heat.
First embodiment of the present invention (water-bearing media/molten system method) provides a kind of method for preparing the solid water-free methylol hydantoin, comprising:
(a) but dewater and heat moisture agitated medium, obtain substantially anhydrous stirred melt, but described moisture agitated medium comprises:
(A) a kind of solute that is selected from following group:
(ⅰ) dihydroxymethyl T10,
(ⅱ) glycolylurea reactant,
(ⅲ) formaldehyde source reactant, or
(ⅳ) any mixture of above-mentioned reactant; With
(B) a kind of catalyzer that adds in case of necessity;
(b) add a kind of reaction-ure mixture in the melt to above-mentioned the stirring, obtain a molten system, described reaction-ure mixture comprises:
(A) (ⅰ) same as described above or different glycolylurea reactant,
(ⅱ) with the identical or different substantially anhydrous formaldehyde source reactant of above-mentioned formaldehyde source reactant, or
(ⅲ) mixture of above-mentioned reactant; And
(B) the same as described above or different catalyzer that add in case of necessity; Wherein molten system comprises (ⅰ) at least a glycolylurea reactant and (ⅱ) the formaldehyde source reactant of at least a dehydration or substantially anhydrous formaldehyde source reactant;
(c) make (ⅰ) at least a described glycolylurea reactant and (ⅱ) the formaldehyde source reactant of at least a described dehydration or substantially anhydrous formaldehyde source reactant react in molten system, remove the water that dereaction generates simultaneously, obtain anhydrous fusion methylol hydantoin; With
(d) methylol hydantoin of solidification of molten.
In second embodiment (combined system method), the preparation method of solid water-free methylol hydantoin is as follows: but in aforesaid moisture agitated medium, make same as described above or different glycolylurea reactant, (ⅱ) with identical or different substantially anhydrous formaldehyde source reactant of above-mentioned formaldehyde source reactant or (ⅲ) mixture of above-mentioned reactant and the reaction-ure mixture reaction that the same as described above or different catalyzer that (ⅳ) adds is in case of necessity formed by (ⅰ); Wherein there is a kind of glycolylurea reactant at least in (ⅰ) and (ⅱ) has a kind of formaldehyde source reactant or substantially anhydrous formaldehyde reaction thing at least; Be heated to the temperature of fusion that is at least methylol hydantoin simultaneously and remove whole substantially water simultaneously; Obtain the fused methylol hydantoin; And the then methylol hydantoin of solidification of molten.
Aforesaid method can interrupter method or semi-continuous process enforcement.
DMDMH is that formaldehyde gives material, is the diformazan acylate of DMH and formaldehyde.MDMH at first generates as intermediate.MDMH itself is a kind of 19%(weight of having an appointment that contains) bonding but the formaldehyde scavenger of the formaldehyde that can dissociate out.The MDMH under connecing and the reaction of formaldehyde obtain DMDMH, in theory its contain 31.9% bonding but the formaldehyde that can dissociate out.
In the methods of the invention, at first provide a kind of moisture reaction medium that stirs.Therefore because initial reaction medium is liquid phase, can use common Liquid-phase reactor for example with the box reactor of stirring, Pfaudlers reactor etc.Do not need for mixing simultaneously and heating the special reaction device that dry reactants or mixture design.
The moisture reaction medium that stirs can be the solution that comprises methylol hydantoin or methylol hydantoin precursor (referred to herein as " solute ") that suspends, dissolves or be stated from a water-bearing media or the solvent, mixture, especially suspension or mixed form.Suitable medium solute is DMDMH; The glycolylurea reactant includes but not limited to DMH and/or MDMH; Formaldehyde source reactant, or any mixture of above-mentioned substance in case of necessity, also can add following catalyzer.
Suitable DMDMH solute comprises, but is not limited to, and DMDMH is as 1,3-dihydroxymethyl-5,5-T10, MDMH such as 1-or 3-methylol-5,5-T10.But the DMH that is suitable for being used as glycolylurea reactant solute in moisture agitated medium comprises, but is not limited to, and T10 is as 5, the 5-T10, monomethylol-5,5-T10,5-ethyl-5-methyl glycolylurea, or the mixture of above-claimed cpd.Suitable MDMH glycolylurea reactant solute comprises, but is not limited to 1-or 3-methylol-5-ethyl-5-methyl glycolylurea, or the mixture of above-claimed cpd.
But the formaldehyde source reactant that is suitable for use as the solute of moisture agitated medium comprises any water-soluble formaldehyde, preferred Paraformaldehyde 96, formalin etc.Paraformaldehyde 96 is for having chemical formula HO(CH
2O)
2-H(wherein n is about 8-100) yuban.
Be suitable for being added to and stir the glycolylurea reactant that melt maybe can stir in the reaction mixture of trembling in the medium and comprise any glycolylurea reactant known in the art, these glycolylurea reactants are being with or without in the presence of the catalyzer, in substantially anhydrous system, in the molten system particularly of the present invention, with substantially anhydrous formaldehyde reaction.Can use the mixture of more than one glycolylurea reactants simultaneously.These glycolylurea reactants comprise, but are not limited to, and DMH is as 5,5-T10, MDMH such as 1-monomethylol-5,5-T10,5-ethyl-5-methyl glycolylurea or its mixture.
The water-content of substantially anhydrous formaldehyde source reactant is not more than 1%(weight).Preferred substantially anhydrous formaldehyde source reactant is a Paraformaldehyde 96.
But be used for agitated medium or be added to glycolylurea and/or the formaldehyde reaction thing in catalyzer generally include, but be not limited to, basic metal or alkaline earth salt are as yellow soda ash, sodium bicarbonate and sodium hydroxide.
But glycolylurea reactant or formaldehyde source reactant that moisture agitated medium or reaction mixture can provide final usefulness to generate the solid water-free methylol hydantoin, but but condition is to have at least a glycolylurea reactant and at least a formaldehyde source reactant to be used for reaction in agitated medium or reaction mixture.
The mol ratio of glycolylurea reactant that reacts in molten system and anhydrous formaldehyde source reactant or substantially anhydrous formaldehyde source reactant is preferably in about 1: 1 to about 1: 2 scope.But moisture agitated medium maybe can stir the mol ratio of melt and glycolylurea reagent to be changed according to DESIGN OF REACTOR, and can change in very wide scope, as long as there are enough materials for example in reactor, to be subjected to, and the stirring of agitator.This DESIGN OF REACTOR is known for the person of ordinary skill of the art.This mol ratio is preferably in about 1 to about 0.1 scope.
But the composition with the methylol hydantoin of the inventive method preparation depends on added methylol hydantoin or glycolylurea in agitated medium, and/or adds the glycolylurea reactant in molten system, and the mol ratio of reactant.For example,, 5-T10) if DMH(is preferred 5 but in agitated medium or as the glycolylurea reactant, and the mol ratio of DMH and formaldehyde source reactant is about 1: 1, then can obtain solid water-free MDMH, particularly 1-or 3-methylol hydantoin.Between about 1: 1 to about 1: 2, can obtain above-mentioned MDMH and DMDMH as above-mentioned mol ratio, particularly 1,3-dihydroxymethyl-5, the mixture of 5-T10.Reach 1: 2 as above-mentioned mol ratio, reaction product is DMDMH substantially entirely.But if methylol hydantoin is arranged or in agitated medium with MDMH, monomethylol-5 particularly, the 5-T10 is as the glycolylurea reactant, and product is generally DMDMH, and particularly 1,3-dihydroxymethyl-5,5-T10.But if methylol hydantoin is arranged or in agitated medium with ethyl-methyl glycolylurea (EMH), particularly 5-ethyl-5-methyl glycolylurea is the glycolylurea reactant, and the mol ratio of EMH and formaldehyde source reactant is about 1: 1, the product that obtains will be hydroxymethyl ethyl methyl glycolylurea (MEMH), particularly 1-or 3-methylol-5-ethyl-methyl glycolylurea.If above-mentioned mol ratio is between about 1: 1 to about 1: 2, the product that obtains is the mixture of MEMH and dihydroxymethyl ethyl-methyl glycolylurea (DMDMH).Reach 1: 2 as above-mentioned mol ratio, reaction product is DMEMH substantially entirely.But methylol hydantoin mixture in the agitated medium or glycolylurea mixture and/or glycolylurea reactant and mol ratio can be regulated, as known for one of ordinary skill in the art or send out the above, and to obtain certain products or product mixture.
In the typical method of one embodiment of the invention, but in reactor, add a certain amount of moisture agitated medium, but perhaps in reactor, directly prepare moisture agitated medium.Then along with the rising of medium temperature, but to moisture agitated medium dehydration, thereby (being that water-content is lower than 1%(weight) finished in dehydration) after, but medium temperature is higher than one or more methylol hydantoins that exist in the moisture agitated medium or the temperature of fusion of glycolylurea.In general, this temperature is at least about 80 ℃, preferably at least about 90 ℃ to about 110 ℃, but but this temperature change with the composition of agitated medium.Usually under reduced pressure dewater, for example to about 200mmHg partial vacuum, dewater in vacuum or about 10.
Melt be can stir then as " tailing " or medium, glycolylurea reactant, substantially anhydrous formaldehyde source or the two mixture added to it.Also can add catalyzer to it.The mol ratio of " tailing " and glycolylurea reactant is generally at about 1 to about 0.1.Can regulate the amount of each component, so that the capacity of reactor is utilized.This point is that those of ordinary skill in the art is known.
All reactants can add simultaneously, also the reactant order can be added or add in batches.
At first, each reactant composition is reacted under molten state, is preferably reacting to about 110 ℃ temperature at least about 80 ℃.At dehydration solute formaldehyde or substantially anhydrous formaldehyde, Paraformaldehyde 96 for example is in the reaction of glycolylurea, owing to the depolymerization of Paraformaldehyde 96 produces reaction water.Can from molten system, remove reaction water with the known any method of those skilled in the art, the preferred method that vacuumizes that adopts.Will obtain anhydrous fusion methylol hydantoin like this, solidify with the crystalline form usually subsequently.
In another embodiment of the present invention, when heating rises to melt temperature, anhydrate but from moisture agitated medium and reaction-ure mixture, remove.
Method of the present invention can periodical operation or the mode of semi continuous operation implement.In semi continuous operation, a part of fusion methylol hydantoin is stayed in the reactor, or transferred in another reactor, as supplying the used tailing of subsequent reactions, rest part is cured as solid water-free methylol hydantoin product then as mentioned above.
Can use this area liquid reactor, mixing device and solidification equipment commonly used in the method for the invention.All dehydrations, heating, mixing and addition step are all undertaken by the operating method of this area routine.
With following embodiment of not having restriction the present invention is described.Except as otherwise noted, all umber and per-cent are all by weight.
Adopt the following analysis method.By with hydroxylammonium salt acidulants reaction assay free formaldehyde.Every moles of formaldehyde discharges 1 mole of hydrogenchloride.By carry out the amount that hydrogenchloride is determined in potentiometric titration with alkali.
Measure the composition (per-cent of DMH, MDMH and DMDMH) of solution with gas-chromatography.
A kind of formaldehyde total amount of measuring in available following two kinds of methods.First method is called the Hantzsch method, by reacting with ammonium acetate and methyl ethyl diketone, bonded formaldehyde is discharged from the T10 ring.Bonded and free formaldehyde and ammonium acetate and methyl ethyl diketone reaction generate 3,5-diacetyl-14 ,-dihydro lutidine.Measure the dimethyl pyrazole piperidine derivatives in the absorption of 413 nanometers, by with the amount of relatively coming to determine formaldehyde of typical curve.Second kind of method of measuring the formaldehyde total amount is the alkali oxidation style.In the solution that contains the excessive hydrogen potassium oxide, use hydrogen peroxide oxidation formaldehyde, generate potassium formiate.With the excessive potassium hydroxide of mineral acid potentiometric titration.
With Karl Fischer commercial measurement water.
Embodiment 1
Add 243.2 gram (3 moles) formalin (37% formalin) to 500 milliliter of four neck round-bottomed flask that magnetic stirrer, stirring rod, thermometer, heating jacket, thermoswitch, condenser and glass stopper are housed.Sodium hydroxide with 0.05 gram 50% is transferred to 8.1 with the pH value of formalin.At room temperature, add 192.2 gram (1.5 moles) DMH, stir the mixture, its temperature rises to 40 ℃.Reaction was carried out 1 hour, obtained monomethylol glycolylurea aq suspension, contained 34.3% water, 1.3% free formaldehyde, and the formaldehyde total amount is 21.5%.
Configuration top stirring rod, thermometer, still head and glass stopper on another 500 milliliter of four neck round-bottomed flask.On still head, dispose the graduated cylinder and the vacuum adapter of thermometer, condenser, collection distillate.By oil bath and thermoswitch controlled temperature.But in this flask, add 183.9 gram methylol hydantoin aq suspension agitated mediums, heating.When temperature reaches 40 ℃, vacuumize (56 mmhg).Temperature is slow to rise to 95 ℃.Water begins to steam in 60 ℃.When temperature reaches 95 ℃, mixture was kept 30 minutes in 56 mmhg, obtain to stir melt.In cold-trap, collect 69.6 gram water altogether.
Then with flask emptying, add 0.38 gram (the solids weight that plan adds 1%) sodium bicarbonate catalyzer.Add 256.3 gram (2 moles) DMH and 125.4 gram (4 moles) 95% Paraformaldehyde 96s in the melt to stirring, temperature is remained on 80 ℃, obtain molten system.
After adding, the temperature of molten system rises to 95 ℃, and insulation is 1 hour under this temperature.Vacuumized (56 mmhg) 45 minutes, and obtained anhydrous fusion methylol hydantoin.
With reactor emptying.The anhydrous methylol hydantoin of fusion is inclined on the aluminium case, obtained white crystalline solid after the cooling.
Analyze solid product, the results are shown in table 1.
Table 1
Formaldehyde total amount 30.8%
Free formaldehyde＜0
Water 0.58
DMH 0.3
MDMH 2.6
DMDMH 96.8
Many methylol hydantoins 0.3
Embodiment 2
Configuration top stirring rod, thermometer, still head and glass stopper on one 500 milliliters four neck flasks.On still head, dispose the graduated cylinder and the vacuum adapter of thermometer, condenser, collection distillate.But add the 111.3 gram 55%DMDMH/MDMH aqueous solution as agitated medium, and 0.35 gram sodium bicarbonate catalyzer to this flask.Stir this medium.With the Paraformaldehyde 96 premixture that added about 268.7 gram (2.1 moles) DMH and 125.8 gram (3.98 moles) 95% in 15 minutes, heating simultaneously, temperature reaches 39 ℃ when finishing so that feed in raw material.Vacuumize (62 mmhg), and keep vacuum, temperature rose to 101 ℃ in 1.5 hours, collected about 50 gram water altogether.
This product is cured as white crystalline solid.Analytical results shows that the formaldehyde total amount is 30.8% in the product, and the content of free formaldehyde is 0.02%, and the content of water is 0.48%.
Embodiment 3(combined system method)
Configuration top stirring rod, thermometer, still head and glass stopper on one 500 milliliters four neck flasks.On still head, dispose the graduated cylinder and the vacuum adapter of thermometer, condenser, collection distillate.Add 53.0 gram water to this flask, add 176.0 gram DMH then, but obtain heavy-gravity but still the paste-like agitated medium that can stir.Add 24.9 gram water again, temperature is risen to 41 ℃.Add 80.5 grams (amounting to 2 moles) DMH again.The temperature of mixture is risen to 53 ℃, and kept this temperature 45 minutes.
With the Paraformaldehyde 96 that added 126.4 gram (4 moles) 95% in 15 minutes.Reheat.When temperature rises to 72 ℃, vacuumize (48 mmhg), anhydrate to remove.In thereafter 2 hours, temperature is risen to 98 ℃, vacuum is risen to 56 mmhg gradually.
Product is solidified.Analytical structure shows that the formaldehyde total amount is 30% in the product, and free formaldehyde content＜0.01%, water-content are 0.8%.
The semi-continuous process of embodiment 4(water-bearing media/molten system)
Repeat the operation of embodiment 1.But after inclining to product on the aluminium foil, 120 gram molten products are stayed in flask, but as agitated medium.Added 0.38 with about 25 minutes and restrain sodium bicarbonate, add the Paraformaldehyde 96 of 256.3 gram (2 moles) DMH and 126.4 gram (4 moles) 95% then.Temperature is remained in 95 ℃ to 97 ℃, be evacuated to 62 millimeters pump plunger shafts gradually, removed with 1 hour 45 minutes again and anhydrate.
Product is solidified.Analytical results shows that the formaldehyde total amount is 30.8% in the product, and free formaldehyde content is 0.01%, and water-content is 0.41%
Embodiment 5(water-bearing media/molten system method)
On one 500 milliliters four neck flasks, dispose overhead, thermometer, still head and glass stopper.On still head, dispose the graduated cylinder and the vacuum adapter of thermometer, condenser, collection distillate.But add the 11.3 gram 55%DMDMH/MDMH aqueous solution as agitated medium to this flask.But the formaldehyde total amount of being somebody's turn to do agitated medium is 18.1%, and free formaldehyde content is 0.83%, and water-content is 45%.In vacuum (56 mmhg) dehydration down, temperature rises to 95 ℃, obtains stirring melt with this medium.Find after analyzing this melt that its formaldehyde total amount is 31.1%, free formaldehyde content is 0.05%, and water-content is 0.82%.
Stir this melt, with the premixture that added the Paraformaldehyde 96 of about 256.3 gram (2 moles) DMH and 126.4 gram (4 moles) 95% in 15 minutes, heating simultaneously is so that the temperature of feeding in raw material when finishing reaches 39 ℃ then.Vacuumize (62 mmhg) then, and keep vacuum.With 1.5 hours temperature is risen to 101 ℃.Collect 50 gram water altogether.
Product is solidified, obtain white crystalline solid.Analysis revealed, the formaldehyde total amount in the product is 31.7%, the content of free formaldehyde＜0.01%, water-content are 0.44%.
All the above-mentioned patents quoted and test method only play reference role in this article.
According to foregoing detailed description, those of ordinary skill in the art can make some changes to the present invention.But these are changed and are not exceeded scope of the present invention.
Claims (23)
1, a kind of method for preparing the solid water-free methylol hydantoin comprises:
(a) but dewater and heat a kind of moisture agitated medium, obtain a kind of substantially anhydrous stirred melt, but described moisture agitated medium comprises:
(A) a kind of solute that is selected from following group:
(i) dihydroxymethyl T10,
(ii) glycolylurea reactant,
(iii) formaldehyde source reactant, or
(iv) any mixture of above-mentioned reactant; And
(B) a kind of catalyzer that adds in case of necessity;
(b) add a kind of reaction-ure mixture in the melt to above-mentioned the stirring, obtain a kind of molten system, this reaction-ure mixture comprises:
(A) (i) same as described above or different glycolylurea reactants,
(ii) identical or different substantially anhydrous formaldehyde source reactant with above-mentioned formaldehyde source reactant, or
The (iii) mixture of above-mentioned reactant; And
(B) the same as described above or different catalyzer that add in case of necessity;
Wherein said molten system comprises the formaldehyde source reactant of (i) at least a glycolylurea reactant and (ii) at least a dehydration or substantially anhydrous formaldehyde source reactant;
(i) at least a described glycolylurea reactant and the formaldehyde source reactant of (ii) at least a described dehydration or substantially anhydrous formaldehyde source reactant are reacted in described molten system, remove the water that dereaction generates simultaneously, obtain anhydrous fusion methylol hydantoin; And
(d) solidify described fusion methylol hydantoin.
2, the described method of claim 1, wherein said solid water-free methylol hydantoin comprises monomethylol dimethyl hydantoin, dihydroxymethyl T10 or its mixture.
3, the described method of claim 1, wherein said dehydrating step (a) is to carry out under the decompression of 10-200mmHg.
4, the described method of claim 1, the temperature of wherein said molten system about 80 ℃ to about 110 ℃ of scopes.
5, the described method of claim 1, wherein said dehydrating step (a) are that heating steps (a) carries out under about 80 ℃ of-110 ℃ of temperature under the 10-200mmHg decompression.
6, the described method of claim 1, the wherein said water that generates in step (c) reaction is removed by the mode of vacuumizing.
7, the described method of claim 1, wherein said method is an interrupter method.
8, the described method of claim 1, wherein said method is a semi-continuous process.
9, the described method of claim 8, wherein step (d) comprising:
(1) the described fusion methylol hydantoin of reservation first part is as stirring melt and repeating step (b)-(d); And
(2) solidify described fusion methylol hydantoin second section.
10, the described method of claim 1, wherein the described glycolylurea reactant in described molten system is a T10, the formaldehyde source reactant of described dehydration or its anhydrous formaldehyde source reactant are Paraformaldehyde 96.
11, the described method of claim 10, wherein said T10 and described Paraformaldehyde 96 added to about 1: 1 mol ratio with about 1: 1.
12, the described method of claim 1, wherein can stir described in the described molten system melt to the mol ratio of described glycolylurea reactant in about 1: 1 to about 1: 10 scope.
13, a kind of method for preparing the solid water-free methylol hydantoin comprises:
(a) for obtaining the fusion methylol hydantoin, but a kind of reactant is blended in a kind of moisture agitated medium to react, described reaction-ure mixture comprises (ⅰ) a kind of glycolylurea reactant, (ⅱ) a kind of substantially anhydrous formaldehyde source reactant or (ⅲ) mixture of above-mentioned reactant, and a kind of catalyzer that (ⅳ) adds in case of necessity; But described moisture agitated medium comprises:
(A) a kind of solute that is selected from following group:
(ⅰ) dihydroxymethyl T10,
(ⅱ) same as described above or different glycolylurea reactant,
(ⅲ) with the above-mentioned substantially anhydrous identical or different formaldehyde source reactant of formaldehyde source reactant, or
(ⅳ) any mixture of above-mentioned reactant; And
(B) a kind of catalyzer that adds in case of necessity;
Wherein there is at least a glycolylurea reactant in (ⅰ) and (ⅱ) has a kind of formaldehyde source reactant or substantially anhydrous formaldehyde source reactant at least;
Be heated to the temperature of fusion that is at least described anhydrous methylol hydantoin simultaneously; And remove whole substantially water simultaneously; And
(b) solidify described fusion methylol hydantoin.
14, the described method of claim 13, the methylol hydantoin of wherein said solid water-free comprises monomethylol dimethyl hydantoin, dihydroxymethyl T10, or its mixture.
15, the described method of claim 13, the wherein said step of anhydrating of removing is carried out under the about 200mmHg decompression of about 10-.
16, the described method of claim 13, wherein said heating is carried out in about 80 ℃ of-110 ℃ of scopes.
17, the described method of claim 13, the wherein said step of anhydrating of removing is carried out under about 10-200mmHg decompression, and described heating steps carries out to about 110 ℃ of scopes in about 80 ℃.
18, the described method of claim 13, wherein said method is an interrupter method.
19, the described method of claim 13, wherein said method is a semi-continuous process.
20, the described method of claim 19, wherein step (b) comprising:
(1) but (ⅰ) keep described fusion methylol hydantoin first part, and repeating step (a) and (b) as agitated medium; With
(2) solidify described fusion methylol hydantoin second section.
21, the described method of claim 13, wherein said glycolylurea reactant is a T10, described formaldehyde source reactant or substantially anhydrous formaldehyde source reactant are Paraformaldehyde 96.
22, the described method of claim 21, wherein said T10 and described Paraformaldehyde 96 with about 1: 1 to about 1: mol ratio react.
23, the described method of claim 13, but the mol ratio of wherein said agitated medium and described glycolylurea reactant is in about 1: 1 to about 1: 10 scope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/887,356 US5252744A (en) | 1992-05-21 | 1992-05-21 | Process for preparing methylolhydantoins |
| US07/887,356 | 1992-05-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1080635A true CN1080635A (en) | 1994-01-12 |
| CN1058263C CN1058263C (en) | 2000-11-08 |
Family
ID=25390977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93105790A Expired - Fee Related CN1058263C (en) | 1992-05-21 | 1993-05-21 | Process for preparing methylolhydantoins |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US5252744A (en) |
| EP (1) | EP0571904B1 (en) |
| JP (1) | JP2604537B2 (en) |
| KR (1) | KR100286244B1 (en) |
| CN (1) | CN1058263C (en) |
| AT (1) | ATE129494T1 (en) |
| AU (1) | AU668719B2 (en) |
| BR (1) | BR9301947A (en) |
| CA (1) | CA2096675C (en) |
| DE (1) | DE69300697T2 (en) |
| DK (1) | DK0571904T3 (en) |
| ES (1) | ES2081162T3 (en) |
| GR (1) | GR3018310T3 (en) |
| HU (1) | HU213034B (en) |
| PL (1) | PL299027A1 (en) |
| RU (1) | RU2105760C1 (en) |
| TW (1) | TW370526B (en) |
| UA (1) | UA27790C2 (en) |
| ZA (1) | ZA933465B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718717A (en) * | 2012-06-15 | 2012-10-10 | 河北亚光精细化工有限公司 | Method for drying solid 1, 3-dihydroxytoluene-5, 5-dimethylhydantoin |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5616722A (en) * | 1995-12-05 | 1997-04-01 | Mcintyre Group, Ltd. | Antimicrobial solution of formaldehyde substituted hydantoin and process for preparation |
| MXPA05001977A (en) * | 2002-08-20 | 2005-09-30 | Lonza Ag | Stable, low free formaldehyde, synergistic antimicrobial compositions of aldehyde donors and dehydroacetic acid. |
| WO2014031537A2 (en) | 2012-08-21 | 2014-02-27 | Lonza, Inc. | Method of scavenging hydrogen sulfide and/or sulfhydryl compounds |
| CN114014811A (en) * | 2021-12-13 | 2022-02-08 | 陕西省石油化工研究设计院 | Preparation method of 1, 3-dimethylol-5, 5-dimethylhydantoin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3987184A (en) * | 1974-06-07 | 1976-10-19 | Glyco Chemicals, Inc. | Dimethylol dimethylhydantoin solution |
| US4908456A (en) * | 1989-04-05 | 1990-03-13 | Takatori Corporation | Process for preparing methylolated hydantoins |
| US5036095A (en) * | 1989-11-14 | 1991-07-30 | Guy Andermann | Therapeutic use of DMDM Hydantoin |
| US5037843A (en) * | 1990-03-05 | 1991-08-06 | The Mcintyre Group, Ltd. | Antimicrobial preservative system and method comprising a formaldehyde substituted hydantoin |
-
1992
- 1992-05-21 US US07/887,356 patent/US5252744A/en not_active Expired - Lifetime
-
1993
- 1993-05-18 ZA ZA933465A patent/ZA933465B/en unknown
- 1993-05-20 HU HU9301479A patent/HU213034B/en not_active IP Right Cessation
- 1993-05-20 CA CA002096675A patent/CA2096675C/en not_active Expired - Fee Related
- 1993-05-20 BR BR9301947A patent/BR9301947A/en not_active IP Right Cessation
- 1993-05-20 AU AU38720/93A patent/AU668719B2/en not_active Ceased
- 1993-05-20 RU RU93005165/04A patent/RU2105760C1/en not_active IP Right Cessation
- 1993-05-20 KR KR1019930008898A patent/KR100286244B1/en not_active IP Right Cessation
- 1993-05-21 PL PL29902793A patent/PL299027A1/en unknown
- 1993-05-21 AT AT93108286T patent/ATE129494T1/en not_active IP Right Cessation
- 1993-05-21 DK DK93108286.1T patent/DK0571904T3/en active
- 1993-05-21 CN CN93105790A patent/CN1058263C/en not_active Expired - Fee Related
- 1993-05-21 JP JP5156030A patent/JP2604537B2/en not_active Expired - Fee Related
- 1993-05-21 DE DE69300697T patent/DE69300697T2/en not_active Expired - Fee Related
- 1993-05-21 EP EP93108286A patent/EP0571904B1/en not_active Expired - Lifetime
- 1993-05-21 ES ES93108286T patent/ES2081162T3/en not_active Expired - Lifetime
- 1993-05-28 UA UA93005389A patent/UA27790C2/en unknown
- 1993-07-22 TW TW082105858A patent/TW370526B/en active
-
1995
- 1995-12-05 GR GR950403429T patent/GR3018310T3/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718717A (en) * | 2012-06-15 | 2012-10-10 | 河北亚光精细化工有限公司 | Method for drying solid 1, 3-dihydroxytoluene-5, 5-dimethylhydantoin |
| CN102718717B (en) * | 2012-06-15 | 2015-03-11 | 河北鑫淘源环保科技有限公司 | Method for drying solid 1, 3-dihydroxytoluene-5, 5-dimethylhydantoin |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69300697T2 (en) | 1996-05-30 |
| CN1058263C (en) | 2000-11-08 |
| CA2096675C (en) | 1997-02-18 |
| KR930023351A (en) | 1993-12-18 |
| DK0571904T3 (en) | 1996-02-05 |
| HU213034B (en) | 1997-01-28 |
| ES2081162T3 (en) | 1996-02-16 |
| CA2096675A1 (en) | 1993-11-22 |
| KR100286244B1 (en) | 2001-04-16 |
| US5252744A (en) | 1993-10-12 |
| TW370526B (en) | 1999-09-21 |
| EP0571904B1 (en) | 1995-10-25 |
| JPH072791A (en) | 1995-01-06 |
| AU668719B2 (en) | 1996-05-16 |
| GR3018310T3 (en) | 1996-03-31 |
| ATE129494T1 (en) | 1995-11-15 |
| PL299027A1 (en) | 1994-01-10 |
| JP2604537B2 (en) | 1997-04-30 |
| HUT64312A (en) | 1993-12-28 |
| ZA933465B (en) | 1994-02-08 |
| BR9301947A (en) | 1993-11-30 |
| EP0571904A1 (en) | 1993-12-01 |
| RU2105760C1 (en) | 1998-02-27 |
| AU3872093A (en) | 1993-11-25 |
| DE69300697D1 (en) | 1995-11-30 |
| UA27790C2 (en) | 2000-10-16 |
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